EP0272896B1 - Vesicle ink compositions - Google Patents

Vesicle ink compositions Download PDF

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Publication number
EP0272896B1
EP0272896B1 EP87311208A EP87311208A EP0272896B1 EP 0272896 B1 EP0272896 B1 EP 0272896B1 EP 87311208 A EP87311208 A EP 87311208A EP 87311208 A EP87311208 A EP 87311208A EP 0272896 B1 EP0272896 B1 EP 0272896B1
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EP
European Patent Office
Prior art keywords
dye
vesicles
composition according
ink
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87311208A
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German (de)
English (en)
French (fr)
Other versions
EP0272896A2 (en
EP0272896A3 (en
Inventor
Ronald Carl Gamble
Michael Lloyd Hair
Sava Rudolf Lukac
Michael Gerard Taylor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nexstar Pharmaceuticals Inc
Original Assignee
Vestar Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Vestar Inc filed Critical Vestar Inc
Publication of EP0272896A2 publication Critical patent/EP0272896A2/en
Publication of EP0272896A3 publication Critical patent/EP0272896A3/en
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Publication of EP0272896B1 publication Critical patent/EP0272896B1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/10—Dispersions; Emulsions
    • A61K9/127—Liposomes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/10—Dispersions; Emulsions
    • A61K9/127—Liposomes
    • A61K9/1271—Non-conventional liposomes, e.g. PEGylated liposomes, liposomes coated with polymers
    • A61K9/1272—Non-conventional liposomes, e.g. PEGylated liposomes, liposomes coated with polymers with substantial amounts of non-phosphatidyl, i.e. non-acylglycerophosphate, surfactants as bilayer-forming substances, e.g. cationic lipids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks

Definitions

  • This invention relates generally to ink compositions and more particularly to ink compositions comprised of vesicles.
  • One embodiment of the present invention is directed to ink compositions comprised of vesicles formulated from, for example, surfactants with a polar group containing two hydrocarbon tails. Therefore, there can be selected for the ink compositions of the present invention, vesicles generated from molecules that form anionic, cationic, nonionic, and zwitterionic components. Vesicles useful in the present invention thus include phospholipid vesicles inclusive of single unilamellar and multilamellar vesicles having a dye associated therewith. Ink compositions comprised of the aforementioned vesicles are useful in printing systems, particularly ink jet printing and possess the desirable characterisics indicated hereinafter including excellent waterfastness and storage stability.
  • Ink jet printers include continuous and so-called “drop-on-demand" ink-jet systems, both of which emit droplets of ink under pressure from a nozzle.
  • ink is ejected in a continuous stream, and the ink that is not used for printing is recirculated.
  • an electromechanical transducer vibrates to break up the steady flow of ink into droplets which are electrically charged and correspond in amount to the signal strengths for the shape of the characters.
  • Drop-on-demand ink jet systems do not recycle ink and rely on piezo-crystal formation to generate a spurt of high pressure to force out drops of ink onto the paper.
  • the bubble-jet system typified by the Hewlett Packard "Thinkjet®” printer, is a variation of the drop-on-demand system, where heat is used to generate bubbles that create a brief pulse of high pressure that propels ink out of a chamber onto the paper.
  • it is necessary that drops be uniform in size, equally spaced from each other, and be formed at a high rate.
  • Z. Kovac and C. Sambucetti Magnetic Ink for Magnetic Ink Jet Printing , Colloids and Surfaces in Reprographic Technology, 1982, the disclosure of which is incorporated herein by reference.
  • Ink jet printer inks are typically formed by dissolving or dispersing dyes or pigments in solvent with additives such as antiseptics and stabilizers.
  • Technical problems encountered with these solvent-based inks include those due to interactions between the ink and the paper surface: after striking the paper, the solvent used in the ink drop spreads before drying.
  • Dye dissolved in the solvent spreads along with the solvent, resulting in a "feathering" effect which degrades resolution since adjacent dots of ink may overlap. Moreover, the dyes in the ink may separate chromatographically in this process, causing an undesirable effect. The solvent and dye also tend to penetrate into the paper. This can result in "print through", where a shadow of the image is observed on the reverse side of the paper sheet. Two-sided printing is not possible under these circumstances.
  • EP-A-036790 discloses a composition comprising simple micelles comprised of surfactants which have a polar head and a single hydrophobic tail, which form particles, without a central aqueous portion, but which have a central organic phase containing not only a dye and but also an organic solvent.
  • the above problems have been treated by modifying the surface of the paper.
  • the paper used in ink jet printing is heavily coated with a variety of materials such as clays designed to reduce or control the spreading of the ink. These coatings, however, increase the cost of the paper and often reduce its aesthetic appeal.
  • coatings which work well with a particular ink jet may not perform well with other marking instruments used in printing apparatus, such as pens or pencils.
  • particulate inks have been used to eliminate feathering, but have been found to settle out of the ink solution over a long period of time and tend to clog the printer nozzle.
  • Water-fastness can be defined as that property of the ink composition which renders it resistant to remove or spreading on the paper when exposed to water after image formation.
  • Lightfastness can be defined as the property of the ink composition which renders it resistant to a change in color when exposed to the light. Improved lightfastness is obtained with the ink composition of the present invention primarily because of the presence of an oil soluble dye.
  • compositions wherein the compositions are stored stable, i.e. the dyes selected are permanently retained within the vesicle and do not settle out on storage.
  • ink compositions that exhibit a high optical density which provides a measure of the quality of the appearance of the ink on paper.
  • a reflectance (optical density) in the range of 1.0 to 1.4 is preferred.
  • An ink composition should contain a dye content in the range of 3-7% of the total ink composition depending on the molar extinction coefficient and molecular weight of the dye.
  • the preferred viscosity range is low, between 1.5 and 1.8 cps (measured against water with a value of 1) (1.5 x 10 ⁇ 3 to 1.8 x 10 ⁇ 3 Pas) for ink jet printers using a piezo-electric driver and 2-3 cps (2 x 10 ⁇ 3 to 3 x 10 ⁇ 3 Pas) for bubble jet printers.
  • the preferred surface tension is 55-60 dynes/cm (0.055 to 0.06 N/m).
  • the ink compositions of the present invention include relative fast drying on the paper (within a few seconds) and water resistance after drying.
  • Successful ink compositions are also chemically stable and have minimal settling out of particles for longer shelf-life, for example 1-2 years. If used in a bubble jet printer, the ink will be subjected to 300°C (bulk temperature approaches 100°C) and must be able to retain the qualities described above under these conditions.
  • the ink must be safe, i.e., contain an approved dye or pigment, and should use relatively inexpensive materials and be easy to manufacture.
  • the flexographic process requires solvents that do not erode rubber rollers and printing plates, thus making the water-based ink composition of the present invention ideal for this process.
  • Further advantages of water inks in the flexographic and rotogravure processes include excellent press stability, printing quality, heat resistance, absence of fire hazard associated with solvents, and the convenience and economy of water.
  • Another object of the present invention is the provision of ink compositions that can be black or another color and which is comprised of vesicles.
  • vesicle ink compositions which enable images of superior resolution.
  • water-based colored or black ink compositions according to the present invention which comprise vesicles, inclusive of unilamellar and multilamellar vesicles having oil soluble dyes, inclusive of lipid-soluble dyes, associated therewith.
  • the present invention provides an aqueous ink composition
  • the ink compositions are comprised of from 70 percent to 95 percent by weight of water; from 5 percent to 30 percent by weight of lipid or other amphiphilic material and dye components.
  • the inks are comprised of from 70 percent to 95 percent by weight of water; from 5 percent by weight to 30 percent by weight ofa phospholipid in the form of unilamellar vesicles and associated therewith an oil soluble dye, inclusive of lipid soluble dyes, present in an amount of from 1.0 percent to 10 percent by weight, and therein the vesicles of the resulting inks are preferably of a diameter of from 100 nanometers to 400 namometers.
  • the method for preparing an ink composition of the invention suitable for use in printing systems comprises the steps of:
  • the phospholipid is replaced by dioctadecyl dimethyl ammonium bromide but the ink and its preparation are otherwise the same as described above.
  • Figure 1 graphically illustrates a typical vesicle-forming amphiphilic molecule.
  • Figure 2 graphically illustrates a bilayer.
  • FIG. 3 graphically illustrates a single unimeller system
  • the ink composition of this invention comprises dye molecules which are soluble in the hydrocarbon bilayer of vesicles formed from surfactants selected from the group consisting of anionic, cationic, zwitterionic and nonionic molecules.
  • the dye molecules are associated with small (40-800 nanometers in diameter, preferably 100 to 400 nanometers) vesicles, in the form of single unilamellar and multilamellar vesicles. Formation of vesicles by the dispersion of anphiphilic compounds in water is fully described in J. Israelachvili, D. Mitchell and B. Ninham, Theory of Self-Assembly of Hydrocarbon Amphiphiles into Micelles and Bilayers , 1976 and D. Evans and B.
  • amphiphiles are molecules with polar and non-polar molecular regions. When dispersed in water, the polar regions are readily solvated while the non-polar fragments of the amphiphile are poorly solvated. Above the critical micelle concentration (CMC), the amphiphiles spontaneously self-assemble to form a variety of mesophases. The CMC is reached when the concentration of the surfactant solute in the bulk of the solution exceeds a limiting value.
  • Such vesicles formed by the dispersion of amphiphilic compounds in water are known in the art and may be prepared, for example, using sonication as described in Liposome Technology , Preparation of Liposomes, Vol. I, Gregoriadis (Ed.), CRC Press, Inc. (1984), or by homogenization as described in EP-A-190,050.
  • Such preparation methods subject the suspension to a high shear force sufficient to generate vesicles of the desired size. These vesicles are capable of solubilizing non-polar dyes, yielding an aqueous-based ink.
  • a typical amphiphilic molecule from which vesicles are formed illustrated in FIG. 1 includes a polar head group 1 and two nonpolar hydrocarbon moieties 3 and 5.
  • the bilayer structure shown in FIG. 2 includes polar head groups 7 and 15 and nonpolar hydrocarbon moieties 9, 11 and 17, 19 respectively.
  • the single unilamellar system shown in FIG. 3, produced by sonication of the mesophases comprises polar head groups 7, 15, nonpolar hydrocarbon tail 9, an inside polar layer 21, a hydrocarbon segment 23 and an outside polar layer 25.
  • vesicles are formed from molecules which contain two hydrophic chains attached to the same hydrophobic head group.
  • Classes of vesicles thus include those formulated from anionic, cationic, non-ionic and zwitterionic head groups. Specific examples include dihexadecyl phosphate (anionic), dioctadecyl dimethyl ammonium bromide (cationic), diacyl glycerides and their ethoxylated derivatives (non-ionic) and phospholipids (zwitterionic).
  • the phospholipid of the vesicles is preferably partially purified (greater than 70% pure) phospholipid, which is less expensive than pure phosolipid and thus decreases the costs of preparing the ink composition, although substantially pure phospholipids may, of course, also be used.
  • substantially pure phospholipids may, of course, also be used.
  • One such phospholipid is soybean L- ⁇ -lecithin.
  • Egg lecithin phosphatidylcholine
  • the general formulation of this embodiment of the ink composition of the present invention is phospholipid comprising 5% to 30% and preferably 5% to 20% by weight of the total ink composition in an aqueous medium such as distilled water.
  • the dye to phospholipid ratio is between 1:1 to 1:10 by weight.
  • To the aqueous medium there may be added 0 to 0.4% by weight of an antioxidant, and 0 to 0.5% by weight of a microbial inhibitor.
  • a preferred antioxidant is L-ascorbic acid, although vitamin E or other antioxidants such as eugenol or ional may also be used.
  • a preferred microbial inhibitor is sodium azide. Further other additives can be incorporated into the inks if needed, such as humectants and the like.
  • Lipid soluble dye molecules typically have a large hydrophobic portion and a smaller hydrophilic region depending on the type of dye. It is believed that the ink molecule partitions into the bilayered membane structure of the vesicle (FIG. 2) during formation of the composition such that the hydrophilic region of the dye molecule is exposed to water, and the hydrophobic region resides within the hydrocarbon portion of the vesicle membrane.
  • the hydrophilic nature of the dye molecule is due in part to the presence of an electric charge generated by protonation or deprotonation of a chemical group in the hydrophilic region of the molecule. This charge may be created or amplified by alterations in the acidity (pH) of the region.
  • pH may enhance the incorporation of dye into the vesicles of the ink composition of the invention.
  • the optimal pH for incorporating dye may vary over a wide range from a pH of 2 to a pH of 10 depending on the specific dye.
  • the optimum pH for incorporating May-Greenwald's dye in lecithin is approximately 2.
  • temperature during preparation of the composition may affect dye incorporation.
  • Dye uptake into the ink may range from 1.0 percent by weight/ml of ink composition to 10 percent.
  • a preferred method of preparing the ink composition of this invention essentially comprises suspending about 5g of the surfactant, and optionally 0 to 0.4% by weight antioxidant and 0 to 0.05% by weight microbial inhibitor in 20 to 25 milliliters water, and sonicating the suspension for 3 minutes at low power (approximately 100 micron peak-to-peak excursion at 20 KH z ). From 0.5g to 5g lipid soluble dye is then added for a dye to phospholipid ratio between 1:1 to 1:10 by weight and the suspension is sonicated at high power (approximately 300 micron peak-to-peak excursion at 20 KH z to form dye-associated vesicles that are 40 to 800 nanometers in diameter.
  • the solution is the centrifuged (2400 r.p.m., 12 inch (305 mm) rotor) for approximately ten minutes and decanted, yielding the ink composition which comprises a dye soluble in the hydrocarbon bilayer of vesicles formed from survactants selected from the group consisting of anionic, cationic, zwitterionic, and nonionic molecules.
  • Non organic solvent is used.
  • the pH was 4.45 and was readjusted to 1.87 with one drop of 6 N HCl followed by a three minute high power sonication (approximately 300 micron peak-to-peak excursion at 20 KHz) to form a violet-coloured ink of May Greenwald's (Giemsa) stain-associated phospholipid vesicles.
  • the mixture was stirred using a vortex stirrer, and then dispersed by sonication on a No. 4 setting for 3 minutes with no cooling.
  • the mixture was divided into aliquots in small (13 x 100 mm) test tubes and each tube was sonicated first at a No. 7 setting for 10 minutes and then at a No. 5 setting for 5 minutes with cooling by a hot (below boiling) water bath. finally, the ink was centrifuged at 2500 r.p.m. for 50 minutes, and decanted.
  • DODAB dioctadecyldimethyl ammonium
  • the viscosity of the vesicle ink compositions was measured using a Cannon Fenske Kinematic viscometer.
  • the percentage of dye uptake was calculated by diluting the unincorporated dye into an organic solvent and measuring optical density with a Carey 14 spectrophotometer.
  • the pH of the ink was determined using a conventional glass electrode pH meter.
  • the test for waterfastness consisted in the comparison of the shape and optical density of the ink before and after water treatment (immersion in water for 10 minutes).
  • dye uptake into the ink was determined to be 6.05% dye and by weight/ml of ink composition, which represents 68% dye uptake.
  • Viscosity was determined to be 3.7 cps (0.0037 Pa.s) (measured against a water standard of 1).
  • the final pH of this ink composition was 1.8, and the ink was of a suitable liquid consistency.
  • the ink composition of this invention can be applied in a number of ways using appropriate printing systems including flexographic, rotogravure presses or electronic devices such as ink jet or bubble jet printers.
  • the ink can be applied by stamps (ink pads) or from rollers or belts to imprint on paper.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Organic Chemistry (AREA)
  • Epidemiology (AREA)
  • Medicinal Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Dispersion Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Molecular Biology (AREA)
  • Biophysics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
EP87311208A 1986-12-18 1987-12-18 Vesicle ink compositions Expired - Lifetime EP0272896B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US944675 1986-12-18
US06/944,675 US4783220A (en) 1986-12-18 1986-12-18 Vesicle ink compositions

Publications (3)

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EP0272896A2 EP0272896A2 (en) 1988-06-29
EP0272896A3 EP0272896A3 (en) 1990-01-17
EP0272896B1 true EP0272896B1 (en) 1994-06-29

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EP87311208A Expired - Lifetime EP0272896B1 (en) 1986-12-18 1987-12-18 Vesicle ink compositions

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US (1) US4783220A (ja)
EP (1) EP0272896B1 (ja)
JP (1) JP2514057B2 (ja)
AT (1) ATE107950T1 (ja)
CA (1) CA1304894C (ja)
DE (1) DE3750160T2 (ja)
ES (1) ES2064321T3 (ja)

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Also Published As

Publication number Publication date
JP2514057B2 (ja) 1996-07-10
CA1304894C (en) 1992-07-14
EP0272896A2 (en) 1988-06-29
ATE107950T1 (de) 1994-07-15
EP0272896A3 (en) 1990-01-17
DE3750160T2 (de) 1994-10-06
DE3750160D1 (de) 1994-08-04
ES2064321T3 (es) 1995-02-01
JPS6485264A (en) 1989-03-30
US4783220A (en) 1988-11-08

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